Chlorine-stable detergent compositions and process for the preparation thereof



3,359,207 CHLORINE-STABLE DETERGENT COMPOSI- TIONS AND PROCESS FOR THEPREPARA- TION THEREOF Thomas M. Kaneko, Trenton, and Irving R. Schmolka,Grosse Ile, Mich assignors to Wyandotte Chemicals Corporation,Wyandotte, Mich a corporation of Filed June 18, 1965, Ser. No. 465,19714 Claims. (Cl. 252-99) Michigan No Drawing.

ABSTRACT OF THE DISCLOSURE Dry, free-flowing chlorine-stable detergentcompositions comprising an alkaline condensed phosphate, a hydratedsodium metasilicate, an active chlorine-containing compound, a nonionicsurfactant, and water are prepared. The compositions are prepared bysequentially mixing the above ingredients as follows: (1) adding anaqueous solution of a nonionic surfactant to an alkaline condensedphosphate whereby simultaneous hydration of the condensed phosphate andabsorption of the surfactant occurs, (2) adding a hydrated sodiummetasilicate to the hydrated condensed phosphate from step (1), (3)reducing the size of the mixture resulting from step (2), and (4) addingan active chlorine-containing compound to the mixture from step (3).

However, heretofore, much difiiculty has accompanied the preparation ofdetergent compositions comprising both an active chlorine-containingcompound and a nonionic surfactant because of the interaction whichgenerally occurs between the two. This interaction generally results indiscoloration-and degradation of the detergent composition with anaccompanying loss in the available chlorine content of the composition.Since a nonionic surfactant possesses wetting properties and an activechlorine compound possesses bleaching, cleaning and sanitizingproperties, it is; desirable to have both compounds present in detergentcompositions.

Several attempts have been made to prepare a detergent compositioncontaining both a chlorine compound and a nonionic surfactant butheretofore all have failed for one reason or another. For example, US.2,895,916 relates to a process for the preparation of detergentcompositions containing an active chlorine compound. Disclosed is use ofa nonionic surfactant in the preparationof the mpositions. It has nowbeen found that although detergent compositions containing an activechlorine compound and a nonionic surfactant may be prepared according toprocess of this patent, the compositions are not stable with respect tothe active chlorine content; that is, within a very short time thestarting available chlorine content decreases to such an extent that forall practical purposes the detergent compositions are chlorine-free.

Now, in aqaordanc'e with this invention, chlorinestable detergentcompositions containing nonionic sur- Examiner 5 3,359,207 Patented Dec.19, 1967 ice factants are prepared by a process requiring specificingredients sequentially admixed in the following manner:

(a) adding an aqueous solution of a nonionic surfactant to an alkalinecondensed phosphate selected from the group consisting of tetrasodiumpyrophosphate and mixtures of tetrasodium pyrophosphate and otherinorganic salts, said mixtures containing at least 50 percent by weighttetrasodium pyrophosphate, whereby hydration of the condensed phosphateand simultaneous absorption of the surfactant occurs;

(b) adding a hydrated sodium metasilicate to the hydrated condensedphosphate with mixing;

(c) reducing the size of the mixture resulting from (b) to a desiredparticle size, and

((1) adding an active chlorine-containing compound to the mixture from(c) whereby a dry, free-flowing, granular product is obtained.

As demonstrated hereinafter, if components other than those stated aboveare employed or if the sequence stated above is not substantiallyfollowed, chlorine-stable detergent compositions are not obtained.

The detergent compositions of this invention comprise four ingredients:an alkaline condensed phosphate, a hydrated metasilicate, an activechlorine-containing compound, and a nonionic surfactant.

Tetrasodium pyrophosphate must be employed as part of the alkalinecondensed phosphate ingredient of the detergent compositions of thisinvention. The phosphate ingredient may comprise 100 percent tetrasodiumpyrophosphate or it may comprise a mixture of tetrasodium pyrophosphateand inorganic salts providing that at least 50 percent of the mixture istetrasodium pyrophosphate. Examples of inorganic salts which may beemployed in admixture with tetrasodium pyrophosphate include sodiumtripolyphosphate, sodium carbonate and sodium sulfate. It has beenfound, and will be demonstrated hereinafter, that if tetrasodiumpyrophosphate is not employed as the phosphate ingredient, either aloneor in admixture as stated, chlorine-stable detergent compositions arenot obtained. Based on 100 parts of detergent composition, 35 to partsof phosphate ingrediem-may be employed, preferably 50 to 60 parts.

Another ingredient of the detergent compositions of this invention is ahydrated sodium metasilicate. Metasilicates serve several functions indetergent compositions which are particularly useful in machineoperations. Besides adding alkalinity to the detergent compositions,they prevent corrosion attack on the washing equipment. Hydratedmetasilicates are employed in the preparation of the compositions ofthis invention since they do not react with nonionic surfactants nor dothey promote agglomeration. Thus, problems previously encountered inusing silicates and metasilicates along with nonionic surfactants, thatis, discoloration and degradation resulting from interaction of thesilicate or metasilicate and surfactant and extensive aging andscreening periods resulting from agglomeration of the product, areovercome by employing the hydrated metasilicates in accordance with thisinvention. Based on parts of detergent composition, five to fifteenparts of hydrated metasilicate, preferably ten parts, may be employed.Sodium metasilicate pentahydrate is the preferred hydrated metasilicateprimarily because it is commercially available.

Another ingredient of the detergent compositions of this invention is anactive chlorine-containing compound. As mentioned above, the activechlorine-containing compound imparts germicidal and bleaching action tothe detergent compositions. Active chlorine-containing compounds whichmay be employed in accordance with this invention include chlorinatedtrisodium phosphate, trichlorocyanuric acid, sodium salt ofdichlorocyanuric acid, potassium salt of dichlorocyanuric acid, sodiumhypochlorite and 1,3-dichloro-5,5-dimethylhydantoin. Based on 100 partsof detergent composition, 5 to 25 parts of active chlorine-containingcompound may be employed. If chlorinated trisodium phosphate isemployed, then from 10 to 25 parts of the chlorine compound is preferredsince the amount of chlorine available in chlorinated trisodiumphosphate is only 0.325 part per part of compound. Much higher amountsof chlorine are available in the chlorinated cyanuric acids and,therefore, when they are employed, from five to ten parts of chlorinecompound is preferred. Generally, the amount of chlorine compoundemployed will depend upon the intended application of the detergentcomposition.

The fourth ingredient of the detergent compositions of this invention isa nonionic surfactant. The use of a surfactant in detergent compositionswhich are to be employed in automatic washing operations is essential togood cleaning and drying since the surfactant serves as a wetting agent.Nonionic surfactants are especially useful in this regard. Not only mustthe surfactant be a wetting agent, it must also not cause or promotefoaming since foaming reduces cleaning efficiency and clogs themachinery. Surfactants which may be employed in the compositions of thisinvention are generally the polyoxyalkylene adducts of hydrophobic baseswherein the oxygen/carbon atom ratio in the oxyalkylene portion of themolecule is at least about 0.5. Those compositions which are condensedwith hydrophobic bases to provide a polyoxyalkylene portion having anoxygen/carbon atom ratio of at least 0.5 include ethylene oxide,butadiene dioxide and glycidol and the like. Ethylene oxide, forexample, is condensed with the hydrophobic base in an amount sufiicientto impart water solubility and surface active properties to the moleculebeing prepared. The exact amount of ethylene oxide condensed with thehydrophobic base will depend upon the chemical characteristics of thebase employed and is readily apparent to those of ordinary skill in theart relating to the synthesis of oxyalkylene surfactant condensates.

Typical hydrophobic bases which can be condensed with ethylene oxide inorder to prepare nonionic surface active agents include monoandpolyalkyl phenols, polyoxypropylene condensed with a base having fromabout one to six carbon atoms and at least one reactive hydrogen atom,fatty acids, fatty amines, fatty amides, alkyl mercaptans and fattyalcohols. The hydrocarbon ethers such as the benzyl or lower alkyl etherof the polyoxyethylene surfactant condensates are also advantageouslyemployed in the compositions of the invention.

Among the suitable nonionic surfactants are the polyoxyethylenecondensates of alkyl phenols having from about six to twenty carbonatoms in the alkyl portion and from about 5 to 30 ethenoxy groups in thepolyoxyethylene radical. The alkyl substituent on the aromatic nucleusmay be octyl, diamyl, polymerized propylene such as propylene tetramerand trimer, isooctyl and many]. The benzyl ethers of the polyoxyethylenecondensates of monoalkyl phenols impart good properties to thecompositions of the invention. A typical product corresponds to theformula:

G (oiHio) .cmomon where R is an alkyl group, and n is from about to 30.

Other suitable water-soluble nonionic surfactants are cogeneric mixturesof conjugated polyoxyalkylene compounds containing in their structure atleast one hydrophobic oxyalkylene chain in which the oxygen/carbon atomratio does not exceed about 0.33 and at least one hydrophilicoxyalkylene chain in which the oxygen/carbon atom ratio is not less thanabout 0.5. Propylene oxide, butylene oxide, amylene oxide and styreneoxide are illustrative of oxyalkylene compounds having an oxygen/ carbonatom ratio not exceeding about 0.33 while ethylene oxide, butadienedioxide and glycidol, as previously pointed out, are illustrative ofoxyalkylene compounds having an oxygen/carbon atom ratio of at leastabout 0.5. Although the hydrophobic chain has an oxygen/carbon atomratio not exceeding about 0.33, it is often advantageous to include inthis chain a small amount of ethylene oxide, that is, up to aboutfifteen weight percent, and likewise in the hydrophilic chain which hasan oxygen/carbon atom ratio not less than about 0.5, it is oftenadvantageous to include a small amount of propylene oxide or butyleneoxide, that is, up to about fifteen weight percent, and theoxygen/carbon atom ratios described herein and in the claims are notintended to preclude such mixtures.

Among the conjugated polyoxyalkylene compounds which can be used in thecompositions of the invention are those which correspond to the formula:

wherein Y is the residue of an organic compound having from about one tosix carbon atoms and one reactive hydrogen atom, n has an average valueof at least about 6.4 as determined by hydroxyl number and m has a valuesuch that the oxyethylene portion constitutes about 10 to weight percentof the molecule. Most of the surface active agents are more particularlydescribed in US. Patent No. 2,677,700.

Other conjugated polyoxyalkylene surface active agents which are mostadvantageously used in the compositions of the invention correspond tothe formula:

3 6 )n( 2 4 )m ]x wherein Y is the residue of an organic compound havingfrom about two to six carbon atoms and containing as reactive hydrogenatoms in which 1: has a value of at least about two, n has a value suchthat the molecular weight of the polyoxypropylene hydrophobic base is atleast about 900 and m has a value such that the oxyethylene content ofthe molecule is from about 10 to 90 weight percent. Compounds fallingwithin the scope of the definition for Y include, for example, propyleneglycol, glycerine, pentaerythritol, trimethylolpropane, ethylenediamine,triethylenetetramine, triisopropanolamine and butylamine. Where Y isethylenediamine, the compounds may be represented by the formula:

ntcimomcimo) wimomcintomi NCHr-CHr-N 3 )1( l )s (C$ I )I(CI IO)H whereinat and y are integers. As already noted, the oxypropylene chainsoptionally, but advantageously, contain small amounts of ethylene oxideand the oxyethylene chains also optionally, but advantageously, containsmall amounts of alkylene oxides having an oxygen/carbon atom ratio ofnot more than about 0.33 such as propylene oxide and butylene oxide.Most of these compounds are more particularly described in US. PatentNos. 2,674,619 and 2,979,528.

Other suitable polyoxyethylene nonionic surface active agents are theethylene oxide adducts of higher aliphatic alcohols having from about 8to 22 carbon atoms in the aliphatic portion, and about 3 to 30 ethenoxyunits in the oxyethylene portion. Typical products are blends of linearfatty alcohols containing an even number of carbon atoms condensed withabout three to nineteen moles of ethylene oxide.

Other suitable nonionic surface active agents are the propylene oxideadducts of condensates of ethylene oxide and higher aliphatic alcoholshaving from about 8 to 22 carbon atoms in the aliphatic portion. Variousratios of ethylene oxide and propylene oxide may be used.

Other suitable nonionic surfactants are the products prepared bycondensing a mixture of ethylene oxide and propylene oxide withaliphatic alcohols having from about 8 to 22 carbon atoms in thealiphatic portion of the alcohol. Various ratios of oxides may beemployed.

Other suitable surface active agents are the polyoxyalkylene surfaceactive agents having heteric polyoxyethylene solubilizing chains. Thesepolyoxyalli'ylene compounds conform to the following generic formula:

wherein Y is the nucleus of an organic reactive hydrogen compoundcontaining 1: reactive hydrogen atoms and having up to six, inclusive,carbon atoms, x is an integer, P is a hydrophobic polyoxyalkylene chainhaving an oxygen/carbon atom ratio of not more than 0.40, the molecularweight of P and the value of at being such that the molecule, excludingE, has a molecular weight of at least about 400 to 900 and up to about25,000, and E is a hydrophilic heteric polyoxyalkylene chain which (1)contains oxyethylene groups and at least five percent by weight ofhigher molecular weight oxyalkylene groups having at least three carbonatoms in their structure, and (2) has an average oxygen/carbon atomratio of greater than 0.40, E being present in the composition to theextent that it constitutes from 5 to 90 weight percent of the totalcomposition. These compositions are more particularly described in US.Patent No. 3,101,374. Mixtures of these compositions and fatty acidphosphates may also be used.

The surfactants are employed in the form of an aqueous solution,generally a 50 percent aqueous solution. The amount of water employed iscritical. The amount of water should only be suflicient to hydrate thephosphate ingredient. Any excess water will detrimentally affect theresulting product since water reacts with the active chlorine-containingcompound to release the chlorine, which in turn reacts with thesurfactant. This causes degradation of the product and loss of availablechlorine. Based on 100 parts of detergent composition, from one to tenparts of surfactant and from one to fifteen parts of water may beemployed provided, however, that the sum total of water and surfactantis at least ten parts. Preferably, five parts of water and five parts ofsurfactant are employed.

As stated before, the detergent compositions of this invention areprepared by a particular sequence of steps. In the first step, anaqueous solution of surfactant is added to a phosphate ingredient. Thesesurfactants may be added in any manner; for example, by pouring orspraying. By adding the surfactant and water to the phosphate ingredientalone, hydration of the phosphate occurs in the presence of thesurfactant which is simultaneously absorbed by the phosphate ingredient.This protects the surfactant from action by the metasilicate andchlorinated compound which are subsequently added. Simultaneous additionof the metasilicate and surfactant, or addition of the metasilicate to aphosphate ingredient which has not absorbed the surfactant, results indiscoloration, degradation and agglomeration of the product.

The second step of the process of this invention involves the additionof the hydrated metasilicate to the hydrated product of the first step.The addition occurs with constant mixing. For the reasons discussedabove, it is essential the metasilicate be added after the phosphateingredient is hydrated and has absorbed the surfactant.

The third step of the process of this invention is a size reductionstep. The mixture from the first or second step is reduced to anydesired size by any conventional means such as crushing, grinding andpreferably screening. It is preferred to reduce the size of the mixturefrom the second step and, therefore, for convenience sake, this step isreferred to as the third step. It is, of course, obvious that if sizereduction occurs on the mixture from the first step, then the sizereduction step is the second step of the process. Generally, when themixture is screened, a S-mesh to 25-mesh screen will be used since thisis the size most appropriate for automatic machine operations.

The fourth step of the process of this invention is the addition of theactive chlorine-containing compound to the screened mixture. In someinstances, this compound may be added along with the metasilicate.However, this is only so when no moisture is present in the hydratedproduct from Step 1. Since it is diflicult to assure that no moisture ispresent, it is advisable to add the chlorine compound after themetasilicate has been added since the metasilicate will absorb anymoisture present.

The process of this invention offers many advantages over knownprocesses. To mention a few, the process of this invention:

(1) provides for the preparation of chlorine-stable detergentcompositions containing nonionic surfactants,

(2) avoids any temperature control problems, and

(3) obviates the need for an aging period.

The following examples illustrate the invention. All parts are by weightunless otherwise stated.

Example I-III Several detergent compositions were prepared in the mannerset forth below. The particular ingredients employed, the amountsthereof and the chlorine stability of the resulting products arepresented in Table l. Chlorine stability is determined by analyzing theavailable chlorine content immediately after preparing the compositionand reanalyzing the chlorine content as days elapse.

The compositions were prepared by first dissolving a surfactant in waterto form a 50 percent solution thereof. The surfactant solution was thensprayed onto mixed tetrasodium pyrophosphate or a mixture of tetrasodiumpyrophosphate and other inorganic salts. As the phosphate ingredientbecame hydrated, all the surfactant was simultaneously absorbed, formingagglomerates of various sizes.

Sodium metasilicate pentahydrate was then added to the agglomerates withcontinuous mixing. The mixed products were then screened through aten-mesh screen and dry, free-flowing granular products were obtained.To these products, an active chlorine-containing compound was admixedwith constant tumbling. Dry, free-flowing granular products wereobtained which retained their dry, free-flowing granular form for overseven months.

1 Commercial product.

I Product prepared by condensing tour moles of propylene oxide with thecondensation product of one mole of a mixture of Gig-Ci. alcohols witheight moles of ethylene oxide.

I Product prepared by condensing three moles of propylene oxide withthecondensation product of one mole of a mixture of O e-C alcohols with sixmoles of ethylene oxide.

4 Plnronic L6i-Product prepared by condensing ethyleneoxide withpolypropylene glycol. Total molecular weight is approximately 2,000, ofwhich about 10 percent is ethylene oxide.

7 Examples lV-X Several detergent compositions were prepared followingthe procedure set forth above. The ingredients employed were:

Parts Parts of tetrasodium pyrophosphate 35 Sodium carbonate 20Surfactant, 50 percent aqueous solution 20 Water, deionized Sodiummetasilicate pentahydrate Chlorinated trisodium phosphate 10 The activechlorine-containing compounds employed were:

Ex. Xl--l,3-dichloro-5,5-dimethylhydantoin EX. XIItrichlorocyanun'c acidEx. Xl'II-sodiurn dichlorocyanurate Ex. XIV-potassium dichlorocyanurate.

All of the detergent compositions of the above Examples XI-XIV wereexcellent dishwashing compositions 10 with stable chlorine contents.

Examples XV-XXI Using the procedure discussed above, various detergentcompositions were prepared using a variety of inorganic builders. In allinstances, the other ingredients employed were:

Parts Sodium metasilicate pentahydrate 10 Chlorinated trisodiumphosphate l0 Surfactant (Pluronic L61), 50 percent aqueous solution 20Water, deionized 5 The inorganic builders used and the results of thechlorine stability test appear in Table 2.

TABLE 2 P Ingredients ans by weight XV XVI XVII XVIII XIX XX XXI gegasodiurg prrophosphate 55 o urn car onate 20 37. 5 5 Sodiumtripolyphosphate 17. 5 6 5 53 20 20 Sodium sulfate. 35 Sodium borate.535 Percent of starting available chlorine content at accelerateddegradation 0.):

After two days 75 75 18 0 1O After six days 57 5s a o o o "6 Percent ofstarting available chlorine content at room temperature alter 130 days88 89.1 47. 5 46. 6 45. 4

Compound became discolored and, therefore, was not further tested.

densate of polypropylene glycol containing about ten percent ethyleneoxide;

Ex. VII-a 5350 molecular weight ethylene oxide condensate ofpolypropylene glycol containing about twenty percent ethylene oxide;

Ex. VIII-a 2450 molecular weight ethylene oxide condensate ofpolypropylene glycol containing about 25 percent ethylene oxide;

Ex. IX-a mixture containing three percent monostearyl acid phosphate and97 percent of the compound employed in Example IV, and

Ex. X-a condensation product of a mixture of ethylene oxide andpropylene oxide with a mixture of C1TC13 alcohols.

All of the detergent compositions of the above examples formulated withno difliculty. They were excellent dishwashing detergents and proved tobe stable with respect to the available chlorine content.

Example XI-XIV Following the procedure set forth under Examples IIII,several detergent compositions were prepared using various activechlorine-containing compounds.

The ingredients employed were:

Parts Tetrasodium pyrophosphate 35 Sodium carbonate 20 Sodiummetasilicate pentahydrate 10 Pluronie L61, 50 percent aqueous solution20 Water, deionized 5 Active chlorine-containing compound 10 45 From thedata presented in Table 2, it is apparent that tetrasodium pyrophosphateis essential to the preparatron of the chlorine-stable detergentcompositions of this invention.

50 Example XXII A detergent dishwashing composition was prepared from:

The composition was prepared following the procedure described inExample I with the exception that the hydrated phosphate product fromStep 1 was screened prior to the addition of the metasilicate. A dry,free-flowing granular product was obtained. After 120 days, 89 percentof the starting available chlorine content remained.

Example XXIII In order to demonstrate the necessity of preparing thedetergent compositions according to the process of this 7 invention,several compositions were prepared varying 9 the sequence ofpreparation. The compositions were prepared with:

(a) This composition was prepared by mixing the tetrasodiumpyrophosphate, sodium carbonate, sodium metasilicate and chlorinatedtrisodium phosphate and then adding the surfactant and water. Slightdiscoloration occurred. Within eight days at accelerated degradation (50C.) analysis showed no detectable amount of available chlorineremaining. After two months at room temperature, only 58 percent of thestarting available chlorine content remained.

(b) This composition was prepared by mixing tetrasodium pyrophosphate,sodium carbonate and sodium metasilicate pentahydrate and then addingthe surfactant and water. After screening, chlorinated trisodiumphosphate was added. Although the product was free-flowing and granular,the available chlorine content decreased rapidly, dropping to 32.7percent of that of the start within six days at 50 C. temperaturestorage.

(c) This composition was prepared by adding the metasilicate andsurfactant simultaneously to the mixture of tetrasodium pyrophosphateand sodium carbonate and then adding the chlorinated trisodiumphosphate. (This procedure is similar to that of U.S. 2,895,916, theonly difference being that metasilicate was used in lieu of sodiumsilicate.) The composition was difficult to formulate since gellingoccurred. The composition was somewhat sticky and tended to cake ataccelerated degradation (50 C.). Extremely rapid degradation wasobserved. There was a slight discoloration of the product within oneday. In five days at 50 C. temperature storage, analysis showed nodetectable amount of available chlorine remaining.

(d) This composition was prepared in the manner set forth in Example 4of U.S. 2,895,916. Dry sodium silicate was used. A dry powder wasobtained only after the product was crushed with an agate mortar andpestle prior to screening. After six days at accelerated degradation (50C.), analysis showed no available chlorine content. Thus, for allpractical purposes, this composition was chlorine-free.

Example XXIV An eggwashing composition was prepared in the manner setforth above. The composition comprised:

Surfactant used in Example 11, 50 percent aqueous solution 10 Sodiummetasilicate pentahydrate 10 Chlorinated trisodium phosphate 22 After120 days, 94 percent of the starting available chlorine content of thecomposition remained. Use of the composition in Kuhl and Seymoureggwashing machines demonstrated superior results over severalcommercially available products.

What is claimed is:

1. A process for the preparation of a chlorine-stable detergentcomposition consisting essentially of, based on 100 parts of saidcomposition, from 35 to 80 parts of an alkaline condensed phosphate,from 5 to 15 parts of a hydrated metasilicate, from 5 to 25 parts of anactive chlorine-containing compound, from 1 to parts of a nonionicsurfactant, and from 1 to parts of water,

or s 10 the sum total of said surfactant and water being at least 10parts which comprises:

(a) adding an aqueous solution of a nonionic surfactant to an alkalinecondensed phosphate selected from the group consisting of tetrasodiumpyrophosphate and mixtures of tetrasodium pyrophosphate and otherinorganic salts other than sodium meta-silicate, said mixturescontaining at least 50 percent by weight tetrasodium pyrophosphate,whereby hydration of the condensed phosphate and simultaneous absorptionof the surfactant occurs;

(b) adding a hydrated sodium metasilicate to the hydrated condensedphosphate with mixing;

(c) reducing the size of the mixture resulting from (b) to a desiredparticle size, and

(d) adding an active chlorine-containing compound selected from thegroup consisting of chlorinated trisodium phosphate, chlorinatedcyanuric acids and alkali metal salts thereof, and1,3-dichloro-5,5-dimethylhydantoin to the mixture from (c) whereby adry, free-flowing, granular product is obtained.

2. The process of claim 1 wherein the surfactant is added in the form ofa 50 percent aqueous solution.

3. The process of claim 1 wherein the surfactant is a compound of theformula Y[(C I-I O),,(C H O) ,H] wherein Y is the residue of an organiccompound having from about two to six carbon atoms and containing xreactive hydrogen atoms in which .1: has a value of at least about two,n has a value such that the molecular weight of the polyoxypropylenehydrophobic base is at least about 900 and m has a value such that theoxyethylene content of the molecule is from about 10 to weight percent.

4. The process of claim 1 wherein the alkaline condensed phosphate istetrasodium pyrophosphate.

5. The process of claim 1 wherein the alkaline condensed phosphate is amixture of tetrasodium pyrophosphate and sodium carbonate.

6. The process of claim 1 wherein the active chlorinecontaining compoundis chlorinated trisodium phosphate.

7. The process of claim 1 wherein the hydrated metasilicate is sodiummetasilicate pentahydrate.

8. A process for the preparation of a chlorine-stable detergentcomposition consisting essentially of, based on parts of saidcomposition, from 35 to 80 parts of an alkaline condensed phosphate,from 5 to 15 parts of a hydrated metasilicate, from 5 to 25 parts of anactive chlorine-containing compound, from 1 to 10 parts of a nonionicsurfactant, and from 1 to 15 parts of water, the sum total of saidsurfactant and water being at least 10 parts which comprises:

(a) adding an aqueous solution of a nonionic surfactant to an alkalinecondensed phosphate selected from the group consisting of tetrasodiumpyrophosphate and mixtures of tetrasodium pyrophosphate and otherinorganic salts other than sodium meta-silicate, said mixturescontaining at least 50 percent by weight tetrasodium pyrophopshate,whereby hydration of the condensed phosphate and simultaneous absorptionof the surfactant occurs;

(b) reducing the size of the mixture resulting from (a) to a desiredparticle size;

(c) adding, with mixing, a hydrated sodium metasilicate to the mixturefrom (b), and

(d) adding an active chlorine-containing compound selected from thegroup consisting of chlorinated trisodium phosphate, chlorinatedcyanurie acids and alkali metal salts thereof, and1,3-dichloro-5,5-dimethylhydantoin to the mixture from (c) whereby adry, free-flowing granular product is obtained.

9. A chlorincastable detergent composition consisting essentially of,based on 100 parts of said composition, from 35 to 80 parts of analkaline condensed phosphate, from 5 to 15 parts of a hydratedmetasilicate, from 5 to 25 parts of an active chlorine-containingcompound, from 1 to 10 parts of a nonionic surfactant, and from 1 to 15parts of water, the sum total of said surfactant and water being atleast parts prepared by:

(a) adding an aqueous solution of a nonionic surfactant to an alkalinecondensed phosphate selected from the group consisting of tetrasodiumpyrophosphate and mixtures of tetrasodium pyrophosphate and otherinorganic salts other than sodium meta-silicate, said mixturescontaining at least 50 percent by weight tetrasodium pyrophosphate,whereby hydration of the condensed phosphate and simultaneous absorptionof the surfactant occurs;

(b) adding a hydrated sodium metasilicate to the hydrated condensedphosphate with mixing;

(c) reducing the size of the mixture resulting from (b) to a desiredparticle size, and

(d) adding an active chlorine-containing compound selected from thegroup consisting of chlorinated trisodium phosphate, chlorinatedcyanuric acids and alkali metal salts thereof, and1,3-dichloro-5,5-dimethylhydantoin to the screened mixture whereby adry, free-flowing granular product is obtained.

10. The composition of claim 9 when the alkaline condensed phosphate istetrasodium pyrophosphate.

11. The composition of claim 9 when the alkaline condensed phosphate isa mixture of tetrasodium pyrophosphate and sodium carbonate.

12. The composition of claim 9 when the surfactant is a compound of theformula Y[C H,,O),,(C;;H O) H] wherein Y is the residue of an organiccompound having from about two to six carbon atoms and containing xreactive hydrogen atoms in which at has a value of at least about two, nhas a value such that the molecular weight of the polyoxypropylenehydrophobic base is at least about 900 and m has a value such that theoxyethylene content of the molecule is from about 10 to weight percent.

13. The composition of claim 9 when the active chlotilting-containingcompound is chlorinated trisodium phosp te.

14. The composition of claim 9 when the hydrated metasilicate is sodiummetasilicate pentahydrate.

References Cited UNITED STATES PATENTS 2,895,916 7/1959 Milenkevich eta1. 252-99 3,154,497 10/1964 Mankowich 252- 3,247,118 4/1966 Matthaei252-99 3,306,858 2/1967 Oberle 252-99 LEON n. ROSDOL, Primary Examiner.2911s, M. WEINBLATT, Assistant Examiner.

1. A PROCESS FOR THE PREPARATION OF A CHLORINE-STABLE DETERGENTCOMPOSITION CONSISTING ESSENTIALLY OF, BASED ON 100 PARTS OF SAIDCOMPOSITION, FROM 35 TO 80 PARTS OF AN ALKALINE CONDENSED PHOSPHATE,FROM 5 TO U5 PARTS OF A HYDRATED METASILICATE, FROM 5 TO 25 PARTS OF ANACTIVE CHLORINE-CONTAINING COMPOUND, FROM 1 TO 10 PARTS OF A NONIONICSURFACTANT, AND FROM 1 TO 15 PARTS OF WATER, THE SUM TOTAL OF SAIDSURFACTNT AND WTER BEING AT LEAST 10 PARTS WHICH COMPRISES: (A) ADDINGAN AQUEOUS SOLUTION OF A NONIONIC SURFACTANT TO AN ALKALINE CONDENSEDPHOSPHATE SELECTED FROM THE GROUP CONSISTING OF TETRASODIUMPYROPHOSPHATE AND MIXTURES OF TETRASODIUM PYROPHOSPHATE AND OTHERINORGANIC SALTS OTHER THAN SODIUM META-SILICATE, SAID MIXTURESCONTAINING AT LEAST 50 PERCENT BY WEIGHT TETRASODIUM PYROPHOSPHATE,WHEREBY HYDRATION OF THE CONDENSED PHOSPHATE AND SIMULTANEOUS BSORPTIONOF THE SURFACTANT OCCURS; (B) ADDING A HYDRATED SODIUM METASILICATE TOTHE HYDRATED CONDENSED PHOSPHATE WITH MIXING; (C) REDUCING THE SIZE OFTHE MIXTURE RESULTING FROM (B) TO A DESIRED PARTICLE SIZE, AND (D)ADDING AN ACTIVE CHLORINE-CONTAINING COMPOUND SELECTED FROM THE GROUPCONSISTING OF CHLORINATED TRISODIUM PHOSPHATE, CHLORINATED CYANURICACIDS, AND ALKALI METAL SALTS THEREOF, AND1,3-DICHLORO-5,5-DIMETHYLHYDANTION TO THE MIXTURE FROM (C) WHEREBY ADRY, FREE-FLOWING GRANULAR PRODUCT IS OBTAINED.